Dinitrobutyrates



Patented Feb. 2, 1954 DINITROBUTYRATES Karl Klager, Monrovia, Calif. No Drawing. Original application December 21,

1951, Serial .880, now

Patent N 0.

2,640,072, dated May 26, 1953. Divided and this application January 9, 1953, Serial No. 330,597

6 Claims. (Cl. 260-478) (Granted under Title 35, U. S. Code (1952),

see. 266) The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This application is a division of applicants copending application Serial No. 262,880, filed December 21, 1951, now Patent No. 2,640,072, granted May 26, 1953, entitled Valerie Acid Derivatives.

This invention relates to new polynitro compounds and to a process for the preparation thereof. Specifically, these new compounds may be represented by the following structural formula:

in which R represents a member of the group including carboxyl and carboxyl derivatives. Compounds in which R represents a carboxyl derivative group, such as an ethyl ester, for example, may readily be converted to 5-hydroxy-4,4-di- 'nitrovaleric acid. However, the acid form lactonizes spontaneously in many cases to form 4,4- dinitrovalerolactone. The nature of the carbonyl derivative group is immaterial since that group is not involved in the formation of the desired compounds. These new compounds may be reacted with sodium methylate to split out formaldehyde and produce the sodium salt of various esters of 4,4-dinitrobutyrate.

As examples of compounds coming within the scope of th above mentioned formula there may be mentioned the following: methyl ester of 5-hydroxy-4,4-dinitrovaleric acid, ethyl 5-hydroxy- 4,4-dinitropentanoate, 5hydroxy-4,4-dinitrovaleric acid, 4,4-dinitrovalerolactone, sodium salt of methyl-4,4-dinitrobutyrate, and the like.

An object of the invention is to provide new nitro compounds. Another object of the invention is to provide a process for the production of new derivatives of valeric acid. A further object is to provide a process for reacting potassium dinitroethanol derivatives of acrylic acid such as, for example, methyl acrylate, ethyl acrylate, acrylonitrile, and acrylamide. Further objects will appear hereinafter.

A new type of polynitro compound is produced by the reaction of equimolar quantities of potassium dinitroethanol and derivatives of acrylic acid as shown in the following equation:

in which R1 represents, for example, an alkyl group. A pH of 6 is maintained during the condensation reactions by neutralizing the KOH formed with acetic acid. The reactions are carried out at room temperature, and yellow oils, scarcely soluble in water, are obtained. By treatment of the oils with 1:1 HCL, the esters are hydrolyzed, and the resulting acid then lactonizes spontaneously to form 4,4-dinitrovalero1actone. The lactone is a light yellow oil boiling at 160 C. under 2 mm. pressure. The lactone crystallizes; it is very soluble in most organic solvents and also in water and is insoluble in petroleum ether and hexane. The examples which follow are illustrative of the various types of valeric acid derivatives that come within the scope of the invention. They are likewise illustrative of the procedures whereby these new. chemical compounds may be synthesized.

Example I.A 34.8 gm. sample of potassium dinitroethanol and ml. of water were placed in a three-necked flask fitted with stirrer, thermometer, and condenser. Then 17 gm. of methyl acrylate was dropped into the mixture within five minutes. While the reaction proceeded, a mixture of 12 gm. acetic acid and 12 gm. water was added over a period of one hour with good agitation. The temperature did not exceed 30 C. during this time. After three hours stirring, nearly all of the potassium salt disappeared. The brown solution which formed was stirred for an additional three hours and allowed to stand overnight. Two layers were formed. After extracting the mixture with ether and Washing with saturated sodium chloride solution, sodium bicarbonate, and again with saturated sodium chloride solution, the ether was removed. The yield was within 30 minutes. which was then collected on a filter and washed 8.93 gm. of methyl 4,4-dinitro--hydroxyvalerate, n =1.4738.

Example II.A round bottom flask provided with a stirrer, thermometer and dropping funnel was charged with 15.8 gm. sodium salt of 2,2-dinitroethanol and 100 ml. Water. A solution of gm. ethyl acrylate and 5.4 gm. glacial acetic acid was added at once while stirring rapidly. The temperature was kept below 30 C. After 8 hours stirring, the mixture was allowed to stand overnight. Two phases were formed. Upon addition of methylene chloride the lower phase contained the ethyl 5-hydr0xy-4,4-dinitrovalerate, which, after drying over sodium sulfate, was freed from solvent in vacuum. The yield was 8.2 ,gm. of a slightly yellow colored oil, which could not be distilled due to decomposition, 1z =l.4666.

Example III.--In the above described apparatus, 15.8 gm. sodium salt of 2,2-dinitroethanol was dissolved in 100 ml. water; 50 ml. methanol was added and while stirring rapidly a mixture of 12.8 gm. butyl acrylate and 5.4 gm. glacial acetic acid was added at once. Thetemperature did not exceed C. After continued stirring at 25 C. for 20 hours, two phases wer formed.

".Themixture .was extracted with methylene chloride and'the methylene chloride solution washed with saturated sodium chloride solution. The methylene chloride solution was dried and the solvent completely evaporated. The residue was butyl 5-hydroxy-4,-dinitrovalerate in the form of a slightly yellow oil which could not be purifled by distillation. Yield 6 gm. n =l/l625.

Example IV.-'A mixture of 8.93 gm. of methyl 4,4 -dinitro:5-hydroxyvalerate and ml. dilute HCl (1:1) was heated for 30 minutes on a steambath. The oil which was insoluble disappeared slowly. The solution was then extracted with .ether and the ether solution washed neutral with saturated sodium chloride and sodium bicarbonate solution. After removing the ether, the residue distilled in an air bath at to C. .under a pressure of 2 mm. mercury. The nearly colorless oil obtained was 4:,4-dinitrovalerolactone which, after crystallization from ether, melted at 78 79" C. The same procedure may be used to form the lactone from other esters.

Example V.-57.2 gm. methyl 5-hydroxy-4A- dinitrovalerate was dissolved in 150 ml. methanol and a mixture of 16 gm. sodium methylate in 80 ml. methanol was added dropwise at a temperatureof-0 to 10 C. The addition was conducted A yellow precipitate formed thoroughly with ether. The compound is the .sodium salt of methyl-eA-dinitrobutyrate.

Example VI.-A flask provided with a thermometer, stirrer and dropping funnel was the salt is soluble.

charged with 9.5 gm. ethyl-4-hydroxy-4,4-dinitrovalerate and 35 ml. methanol. The mixture was cooled to 0 C. and 30 ml. 10% sodium methylate in methanol was added slowly. From the brown solution formed, yellow crystals precipitated which were collected on a filter and washed with a mixture of methanol and ether. Yield 9.2 gm, M. P. 166 C. dec. of sodium ethyl- 4,4-dinitrobutyrate.

Example VII.--In the apparatus described above the amount of 8 gm. butyl-5-hydroxy-4A- dinitrovalerate was dissolved in 12 ml. methanol.

The mixture was cooled to 0 C. and 20 ml. 10% sodium methylate in methanol was added slowly. A'bright yellow precipitate was formed almost immediately. By warming at room temperature, After cooling to -l5 C. the crystalline salt was filtered off and washed with a mixture of methanol and ether. The yield was 6.9 gm., M. P. C. dec. of sodium butyl-4A- dinitrobutyrate.

The nitrated aliphatic compounds resulting from the above described process are valuable explosives ingredients since they are uniform and relatively stable. The compounds of this invention also exhibit utility =as-intermediates from which a variety of nitrated products may be prepared.

Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is therefore to be understood that withinthe scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed is:

1. Sodium methyl-4A-dinitrobutyrate.

2. Sodium ethyl-4,4-dinitrobutyrate.

3. Sodium butyl-4,4-dinitrobutyrate.

4. Compounds having the formula:

r it er N 02 H H No references cited. 

1. SODIUM METHYL-4,4-DINITROBUTYRATE. 